JPH02179649A - Absorbent for infrared ray and image forming material - Google Patents

Abstract

PURPOSE:To obtain an image forming material capable of generating heat by the absorption of light energy and forming a distinct three-dimensional picture image by using an absorbent for infrared rays consisting of a specified compound oxide. CONSTITUTION:The absorbent for infrared rays consists of a compound oxide consisting primarily of an oxide of Sn, Sb, or In. A red crayon is obtd. by mixing, for example, wax, pigment, a coloring material, and above-mentioned absorbent in a desired proportion, and the mixture is heated, mixed, and poured into a mold. A picture image is formed by hand with the obtd. crayon on a heat-expansive sheet provided with a heat expansive layer contg. heat-expansive minute spheres on one side of a sheet-shaped base material, and the picture image is exposed to light. Thus, the picture image part of the sheet rises and a red three-dimensional picture image is formed. Since clouding of color is caused scarcely when the absorbent is used, so a distinct three-dimensional picture image is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an infrared light absorber and an image forming material used, for example, when forming a three-dimensional image on a thermally expandable sheet.

[Conventional Technique #I] Conventionally, a desired image is formed on the surface of a thermally expandable sheet using an image forming material with high light absorption, and then the surface is irradiated with light, whereby the image area is changed due to the difference in light absorption. A method is known in which a three-dimensional image is formed by selectively heating and elevating only the surface (Japanese Patent Publication No. 59-35359, etc.). Since the image forming material used in this method must have high light absorption, it is usually black or brown. That is, even if an image was formed using image forming materials of red, blue, green, yellow, etc. and irradiated with light, a three-dimensional image could not be obtained because these image forming materials had low light absorption. Therefore, when it is desired to colorize the resulting stereoscopic image, methods are being explored in which, after forming the stereoscopic image, a color foil of a desired color is transferred to the stereoscopic image area.

However, this method requires a transfer operation after three-dimensional image formation, resulting in long and complicated operation steps. Also,
If a color foil is transferred without completely covering an image area of black or the like, the underlying color will be exposed and the appearance will be poor. Therefore, the applicant has proposed an image forming material in which a material such as carbon black that can absorb light energy and generate heat is added to a colored image forming material used in an electrophotographic image forming apparatus, and has already filed an application. (Patent Application No. 183556/1982).

[Problems to be Solved by the Invention] However, in the above-mentioned colored image-forming materials, when a sufficient amount of carbon black is added to make the thermally expandable sheet bulge, the colors may become cloudy, especially in white, yellow, etc. The turbidity will become stronger. Therefore, even when it is desired to emphasize colors or use colors such as white or yellow, the desired clear colors cannot be obtained.

The present invention has been devised in view of the above circumstances, and its technical object is to provide an infrared light absorber and an image forming material that absorb light energy and generate heat.

[Means for Solving the Problems] The infrared light absorber according to the first invention is made of a composite oxide whose main component is an oxide of tin, antimony, or indium.

The image forming material according to the second invention comprises a vehicle, a colorant, and an infrared light absorber whose main component is an oxide of tin, antimony, or indium.

The image forming material according to the third invention includes a thermoplastic resin, 1
It consists of a single color agent and an infrared light absorber whose main component is an oxide of tin, antimony, or indium, and is in the form of a fine powder.

The image forming material according to the fourth aspect of the present invention is composed of a thermoplastic resin and an infrared light absorber whose main component is an oxide of tin, antimony, or indium, and is in the form of a fine powder.

Here, the oxide of tin, antimony, or indium means a simple oxide of tin, antimony, or indium, or a composite oxide containing tin, antimony, or indium as a main component.

In addition, vehicle refers to the component that serves as a matrix.
Colorants refer to substances mainly composed of organic substances, and colorants refer to substances composed of pigments, dyes, etc.

[Function] The infrared light absorber according to the first invention absorbs light energy and generates heat when irradiated with light. Therefore, in the image forming materials according to the second to fourth inventions in which this infrared light absorber is blended, the surrounding vehicle etc. are gradually heated by the infrared light absorber, which generates heat upon being irradiated with light, and the entire body is heated. The body becomes overheated.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

(Example 1) This example is an example of a red crayon as an image forming material containing an infrared light absorber. This red crayon A is
5 parts of antimony-containing tin oxide (manufactured by Sumitomo Cement Co., Ltd., hereinafter the same) as an infrared light absorber is mixed with 100 parts by weight of conventional red crayon B (manufactured by Miyazaki Kogyo Co., Ltd.). It is configured as follows. Conventional red crayon B contains 50 thick parts of wax (real wax, saturated/unsaturated fat I!! and its ester), 35 flffkf'A of pigment (talc, clay, titanium oxide), and color vJ (red No. 202 (I).
J'/-lupine BCΔ) and Red No. 204 (Rake Red BCΔ) 15 mm part (see Group 1).

Table 1 Red crayon A of this example was manufactured as follows. First, wax, pigment, coloring material, and infrared light absorber are blended in the above proportions and heated. Then, the wax is fluidized and mixed uniformly, and the molten wax is poured into a mold and cooled. After cooling, the product is removed from the mold to obtain the red crayon 8 of this example.

A three-dimensional image was formed using this red crayon 8 using a thermally expandable sheet (manufactured by Minolta Business Machine Sales Co., Ltd., hereinafter the same). Note that the thermally expandable sheet has a thermally expandable layer containing thermally expandable microspheres on one surface of a sheet-like base material. First, a desired image was formed on a thermally expandable sheet by hand with red crayon A. Then, the thermally expandable sheet was heated using a special light irradiation device M (manufactured by Minolta Business Machine Sales Co., Ltd.).
The same applies below). As a result, only the portion of the thermally expandable sheet corresponding to the image was raised, and a good red three-dimensional image could be formed. The reason why we were able to form a three-dimensional image in this way is that the antimony-containing tin oxide contained in Red Crayon A absorbs light energy and generates heat, and this heat generation causes the thermally expandable microspheres to heat up. The thermal expansion layer rises and becomes three-dimensional.

Incidentally, although the same procedure was carried out using the conventional red crayon B, it was not possible to form a three-dimensional image.

The red crayon A of this example and the conventional red crayon B were tested using a spectrophotometer (“3” manufactured by Hitachi, Ltd.).
The light reflectance was measured using a 40-inch self-recording spectrophotometer (the same applies hereinafter). As shown in FIG. 1, the red crayon A of this example was in the near-infrared region (630-1800n
In m), the reflectance was lower, and it was confirmed that the light absorption property was better than that of the conventional red crayon B. That is, the red crayon A of this example contains antimony-containing tin oxide, and it was confirmed that antimony-containing tin oxide is effective as an infrared light absorber.

(Example 2) This example is an example of a yellow crayon. This yellow crayon C is different from the conventional yellow crayon D (manufactured by Miyazaki Kogyo Co., Ltd. >1
00 weight ffi parts, tin-containing indium oxide as an infrared light absorber (manufactured by Sumira Cement Co., Ltd., the same hereinafter)
It contains 10 parts by weight. Conventional Yellow Crayon D contains 50 parts by weight of wax (real wax, saturated/unsaturated fatty acids and their esters), 25 parts by weight of pigments (talc, clay, titanium oxide), and coloring material (Yellow No. 4 (dirt lazine and titanium oxide)). Mixture) Composed of 251 peaks (Table 1
reference).

The yellow crayon C of this example was produced in the same manner as in Example 1 above.

Yellow crayon C of this example and conventional yellow crayon D
As in Example 1, an image was formed using a thermally expandable sheet and irradiated with light using a light irradiation device to make it three-dimensional. However, in the case of the conventional yellow crayon D, it was not possible to form a three-dimensional image, whereas in the case of the yellow crayon C of this example, a good yellow three-dimensional image could be formed.

The light reflectance of the yellow crayon C of this example and the conventional yellow crayon D was measured using a spectrophotometer in the same manner as in Example 1 above. As shown in FIG. 2, the yellow crayon C of this example was produced in the near infrared region (7
00 to 1800 nm), and it was confirmed that the light absorption property was better than that of the conventional yellow crayon D. That is, the red crayon A of this example contains tin-containing indium oxide, and it was confirmed that tin-containing indium oxide is effective as an infrared light absorber.

(Example 3) This example is an example of a red printing ink as an image forming material.

The printing ink of this example is a red ink consisting of a vehicle with the following composition and a W coloring agent, and a 5-layered portion of tin-containing indium oxide as an infrared light absorber is whitened on the 100-layeredmost portion of the red ink, which consists of a vehicle with the following composition and a W coloring agent, and is uniformly distributed. It was formed in a dispersed manner.

(Composition of red ink) Brilliant carmine 6 [35% by weight] Clay 35% by weight ethyl hydroxyethyl cellulose (EHEC) 5% by weight Rosin pentaerythritol ester 10% by weight Mineral spirit 20% by weight #100 solvent (aromatic hydrocarbon solvent) 20% by weight Cellosolve 5% by weight Using the printing ink of this example, a desired image was printed on a thermally expandable sheet by a screen printing method. After the printing ink was dried, it was irradiated with light using a light irradiation device. As a result, only the image portion of the thermally expandable sheet formed by the printing ink was raised, making it possible to form a clear red three-dimensional image. Although the same procedure was carried out using a conventional red ink that does not contain an infrared light absorber, it was not possible to form a three-dimensional image.

(Example 4) This example is an example of a blue printing ink as an image forming material.

The printing ink of this example consisted of 100 parts by weight of indigo ink consisting of a vehicle and colorant having the following composition, and 3 layers of antimony-containing tin oxide as an infrared light absorber! It is formed by blending 1 part and uniformly dispersing it.

(Composition of blue ink) Phthalocyanine blue (β type) 3% by weight Titanium oxide (rutile type) 25% by weight Vinyl chloride/vinyl acetate copolymer resin 20% by weight Acrylic resin 5% by weight cyclohexane 10% by weight #100 solvent (
Aromatic hydrocarbon solvent) 33% by weight Isophorone 3% Dioctyl phthalate (DOP) i% IS Using the indigo printing ink of this example, as in Example 3 above,
A desired image was printed on the thermally expandable sheet by a screen printing method. Then, after the printing ink had dried, it was irradiated with light using a light illumination device. As a result, only the image portion of the thermally expandable sheet formed by the printing ink was raised, and a clear indigo three-dimensional image could be formed.

Although the same procedure was carried out using a conventional indigo ink containing no infrared light absorber, it was not possible to form a three-dimensional shadow.

(Example 5) This example is an example of paint as an image forming material.

The paint used in this example was the commercially available paint emerald green (Sony Corporation 1rLiQLJ it
exJ) 1 part of 10011J was blended with 3 parts of tin-containing indium oxide as an infrared light absorber and uniformly dispersed.

A desired image was formed on a thermally expandable sheet using the paint of this example, and after the paint had dried, it was irradiated with light using a backlight irradiation device. As a result, only the image portion of the thermally expandable sheet formed with the paint was raised, making it possible to form a clear emerald green three-dimensional image. Although the same procedure was carried out using a conventional emerald green paint that does not contain an infrared light absorber, it was not possible to form a three-dimensional image.

Similarly, when using conventional paints of different colors such as cobalt blue and yellow medium Anne (12i1 Newsletter) mixed with tin-containing indium oxide or antimony-containing tin oxide, thermally expandable sheets can be made into three-dimensional shapes. I was able to convert it into

(Example 6) This product 11#iW4 is an example of a white toner used as a WA@ agent in an electrophotography method.

The white toner of this example has the following composition, and contains 0.5 to 5 parts by weight of tin-containing indium oxide as an infrared light absorber.

(Composition of white toner) Styrene-acrylic copolymer resin 100 parts by weight Titanium oxide (white pigment) 30 parts by weight Tin-containing indium oxide (infrared light absorber) 0.5 to 51 parts Low molecular weight polypropylene 2.5 heavy ffi parts, quaternary ammonium, 2 parts by weight, styrene-amine acrylic copolymer resin, 6 parts by weight, and the amounts of tin-containing indium oxide: 0.5 parts by weight, 1.0jlffi parts, 2.0 parts by weight, 5. Four types of products containing 0 parts by weight were prepared and used to form a three-dimensional image on a thermally expandable sheet, and the raised height and color tone of the resulting three-dimensional image were examined. Image formation with white toner is
This was done using an electrophotographic copying machine (manufactured by Minolta Camera Co., Ltd.), and then the image was made three-dimensional using a light irradiation device.

The same procedure was carried out for Comparative Example 1 in which no tin-containing indium oxide was blended, and Comparative Example 2 in which carbon black was blended in place of the tin-containing indium oxide.

(The following is a blank space) As shown in Table 2, the tin-containing indium oxide of this example was mixed with 0.5 parts by weight, 1.0 parts by weight, or 2 parts by weight. OF
When 811tM is mixed, both are 0°5 to 0.85
A sufficient raised height of mm was obtained, and clear white color without turbidity could be reproduced. In addition, tin-containing indium oxide was added to 5.
When 0171 parts were blended, the height of the protuberance was 0.9 mm, and although there was some turbidity, a white color almost the same as the primary color could be reproduced.

On the other hand, in the case of Comparative Example 1, although a clear white color could be reproduced, no ridges were formed and a three-dimensional image could not be formed.In addition, in the case of Comparative Example 2, the ridge height was 0.9 mm. Although sufficient three-dimensionality was possible, the color turned gray and white could not be reproduced.

(Example 7) This example is an example of a red toner composed of the following composition, in which tin-containing indium oxide as an infrared light absorber is
．． It is blended in an amount of 5 to 5 parts by weight.

(Composition of red toner) 100 parts by weight of styrene-acrylic copolymer resin red pigment (“l-i tho l5car” manufactured by BASF)
let [)3700J) 5 parts by weight Tin-containing indium oxide (infrared light absorber) 0.5 to 5 parts by weight Low molecular weight polypropylene 21 M parts Styrene
Four types of aminoacrylic copolymer resin 11 iffi parts and tin-containing indium oxide blended amounts of 0.5 mm parts, i, amms, 2.0 weight FIJ, and 5.0 mm parts were prepared, and these were used. A three-dimensional image was formed on a thermally expandable sheet, and the raised height and achromaticity of the resulting three-dimensional image were examined. Formation of liljm using red toner and three-dimensional image formation were performed in the same manner as in Example 6 above.

The same procedure was carried out for Comparative Example 3, in which no tin-containing indium oxide was blended, and Comparative Example 4, in which 1.0 weight φ part of carbon black was blended instead of tin-containing indium oxide.

As shown in Table 3, when the tin-containing indium oxide of this example was blended at 0.5 parts, 1.0 parts by weight, 2.0 mm parts, or 5.0 parts by weight, all cases were 0. .5～
A sufficient raised height of 0.9 mm was obtained, and a clear primary color of red without turbidity could be reproduced.

On the other hand, in the case of Comparative Example 3, although a clear red color could be reproduced, there was no elevation at all, and a three-dimensional image could not be formed. In addition, in the case of Comparative Example 4, the height of the protrusion was Q, gmm, and although sufficient three-dimensionality was possible, the color was black and cloudy red.

(Example 8) This example is an example of a blue toner composed of the following composition, in which antimony-containing tin oxide as an infrared light absorber was
．． It is blended in an amount of 5 to 5 parts by weight.

(Composition of blue toner) 100 parts by weight of styrene-acrylic copolymer resin blue pigment (“Heil togenBlu” manufactured by BASF)
e L7020J) 51f 11 parts Antimony-containing tin oxide (infrared light absorber) 0.5 to 5 parts by weight Styrene-amine acrylic copolymer resin 1 polymer part Low molecular weight polypropylene 2 parts by weight And the amount of antimony-containing tin oxide Four types of 0°5 parts by weight, 1.0 parts by weight, 2.0 parts by weight, and 5.0 mm parts were prepared, and these were used to form a three-dimensional image on a thermally expandable sheet. The height and color tone of the 3D images were investigated. Formation of an image using blue toner and three-dimensionalization of the image were performed in the same manner as in Example 6 above.

The same procedure was carried out for Comparative Example 5, in which no antimony-containing tin oxide was blended, and Comparative Example 4, in which 1.0 mm part of carbon black was blended instead of antimony-containing tin oxide.

(The following is a blank space) Table 4 As shown in Table 4, the antimony-containing tin oxide of this example was mixed at 0.5 parts by weight, 1.0 parts by weight, 2, Of! [
When 1 part or 5.0 parts by weight of ffi was added, a sufficient raised height of 0.5 to 0.9 mm was achieved in both cases, and a clear blue primary color without turbidity could be reproduced.

On the other hand, in the case of Comparative Example 5, although a clear blue color could be reproduced, Q was not raised by more than 1 mm, and a three-dimensional image could hardly be formed. In addition, in the case of Comparative Example 6, the height of the protrusion was Q, gmm, and although sufficient three-dimensionality was possible, the color was black and cloudy blue.

(Example 9) This example is an example of a toner with excellent infrared light absorption.

This infrared light absorbing toner has the following composition, and contains 5 parts by weight of tin-containing indium oxide, which is an infrared light absorber.

(Composition of infrared light absorbing toner) 100 parts by weight of styrene-acrylic copolymer resin 5 parts by weight of tin-containing indium oxide (infrared light absorber) 2 parts by weight of low molecular weight polypropylene 2 parts by weight of styrene-amine acrylic copolymer resin Part 1 The infrared light-absorbing toner of this example can be used as an image-forming material for forming a three-dimensional image on a thermally expandable sheet by mixing it with a desired color toner.

Three types of infrared light-absorbing toner of this example were blended with 5 parts by weight, 10 parts by weight, and 20 parts by weight, respectively, to 100 parts by weight of the red toner having the following composition. These were used to form a three-dimensional image on a thermally expandable sheet, and the height and color tone of the resulting three-dimensional image were examined. Image formation and three-dimensional image formation using these mixed toners were carried out in the same manner as in Example 6 above.

In addition, Comparative Example 7 contains no infrared light-absorbing toner, and Comparative Example 8 contains carbon black (manufactured by Mitsubishi Kasei Corporation) instead of the infrared light-absorbing toner.
The same procedure was carried out for a black toner containing 5 parts by weight of 31ac #40J) containing 101 Obe Shidara.

(Composition of Red 1 to 1) 100 parts by weight of styrene-acrylic copolymer resin
tD3700J) 5 parts by weight Low molecular weight lubricating polypropylene Double layer Styrene-aminoacrylic copolymer resin Single layer Table 5 As shown in Table 5, the infrared light-absorbing toner of this example was When blending 10 parts by weight, 10 parts by weight, or 20 parts by weight, a sufficient raised height of 0.6 to 069 mm was obtained in all cases, and a clear red color without turbidity could be reproduced.

On the other hand, in the case of Comparative Example 7, although a clear red color could be reproduced, there was no elevation at all, and a three-dimensional image could not be formed. Further, in the case of Comparative Example 8, the height of the protrusion was 0.75 mm, and although sufficient three-dimensionality was possible, the color was black and cloudy red.

(Example 10) Similar to Example 9, this example is an example of a toner with extensive infrared light absorption. This infrared light absorbing toner has the following composition, and contains 5 parts by weight of antimony-containing tin oxide, which is an infrared light absorber.

(Composition of infrared light absorbing toner) Styrene-acrylic copolymer resin 1001 parts Low molecular weight polypropylene 2 parts by weight Styrene-
1 part by weight of amine acrylic copolymer resin 5 parts by weight of antimony-containing tin oxide (infrared light absorbent) and 100 parts by weight of a white toner having the following composition: 3f! by blending 5 parts by weight, 10 parts by weight, and 20 parts by weight of toner! Type U was prepared, and the raised height and color tone of the resulting three-dimensional image were examined in the same manner as in Example 9 above.

The same procedure was carried out for Comparative Example 9, in which no infrared light-absorbing toner was blended, and Comparative Example 10, in which 10 parts by weight of the same black toner as in Comparative Example 8 was blended instead of the infrared light-absorbing toner. Ta.

(Composition of white toner 1 Styrene-acrylic copolymer resin 100% titanium (white pigment) 5-fold positive quaternary ammonium 2-fold positive low molecular I polypropylene 2.5-fold positive styrene-aminoacrylic copolymer Resin 6 parts Table 6 As shown in Table 6, when the infrared light-absorbing toner of this example was blended with 5 parts, 10 parts by weight, or 20 parts by weight, 0.5 parts by weight in each case. A sufficient height of upheaval of ~0.8 mm was obtained, and clear white color without turbidity could be reproduced.

On the other hand, in the case of Comparative Example 9, although a clear white color could be reproduced, there was no elevation at all, and it was not possible to form a three-dimensional image border. In addition, in the case of Comparative Example 10, the height of the protrusion was 0.7 mm.
Although sufficient three-dimensionality was possible, it turned out to be gray.

[Effects of the Invention] The infrared light absorber according to the first invention can absorb light energy and generate heat. Therefore, the image forming materials according to the second to fourth inventions in which this infrared light absorber is blended can generate heat when irradiated with light, and the influence of the infrared light absorber on the color tone is extremely large. few. Therefore, when a three-dimensional image is formed using a thermally expandable sheet, image forming materials of various colors can be used.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the measurement results of the spectral reflectance of the red crayon according to Example 1, and FIG. 2 is a graph showing the measurement results of the spectral reflectance of the yellow crayon according to Example 2. Patent applicant Minolta Camera Co., Ltd.

Claims (4)

[Claims] (1) An infrared light absorber comprising a composite oxide whose main component is an oxide of tin, antimony, or indium. (2) An image forming material comprising a vehicle, a colorant, and an infrared light absorber whose main component is an oxide of tin, antimony, or indium. (3) An image forming material comprising a thermoplastic resin, a colorant, and an infrared light absorber whose main component is an oxide of tin, antimony, or indium, and which is in the form of a fine powder. (4) An image forming material comprising a thermoplastic resin and an infrared light absorber whose main component is an oxide of tin, antimony, or indium, and which is in the form of a fine powder.